(1S,5R)-3,3,7,9,9-pentamethyl-5-<(phenylmethoxy)methyl>-2,4-dioxaspiro<4.4>non-6-ene | 171866-88-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1S,5R)-3,3,7,9,9-pentamethyl-5-<(phenylmethoxy)methyl>-2,4-dioxaspiro<4.4>non-6-ene
• 英文别名: (4S,5S)-2,2,7,9,9-pentamethyl-4-(phenylmethoxymethyl)-1,3-dioxaspiro[4.4]non-6-ene
• CAS: 171866-88-9
• 化学式: C₂₀H₂₈O₃
• 分子量: 316.441
• InChiKey: YIAQXOGISWAIEX-FXAWDEMLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,5R)-3,3,7,9,9-pentamethyl-5-<(phenylmethoxy)methyl>-2,4-dioxaspiro<4.4>non-6-ene 在 氢氧化钾 、 臭氧 、 三苯基膦 作用下， 生成
  参考文献：
  名称：

  Efficient Intramolecular C-H Insertion by an Alkylidene Carbene Generated from a Vinyl Chloride

  摘要：

  It is observed that chloride 4 on exposure to sodium bis(trimethylsilyl)amide smoothly generates the cyclopentene 5, by insertion of the intermediate alkylidene carbene into the methine C-H. Chloride 4 is prepared in several steps from L-tartaric acid. On ozonolysis and subsequent aldol condensation, 5 is transformed into 1, a synthon for the A ring of taxol 2.

  DOI：

  10.1021/jo00125a050
• 作为产物：
  描述：

  (4S,5R)-4-benzyloxymethyl-2,2-dimethyl-1,3-dioxolane-5-carboxaldehyde 在 正丁基锂 、 copper(I) bromide dimethylsulfide complex 、 sodium acetate 、 sodium hexamethyldisilazane 、 sodium hydride 、 二异丙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 正己烷 、 二氯甲烷 、 甲苯 、 paraffin 为溶剂， 反应 52.92h， 生成 (1S,5R)-3,3,7,9,9-pentamethyl-5-<(phenylmethoxy)methyl>-2,4-dioxaspiro<4.4>non-6-ene
  参考文献：
  名称：

  Efficient Intramolecular C-H Insertion by an Alkylidene Carbene Generated from a Vinyl Chloride

  摘要：

  It is observed that chloride 4 on exposure to sodium bis(trimethylsilyl)amide smoothly generates the cyclopentene 5, by insertion of the intermediate alkylidene carbene into the methine C-H. Chloride 4 is prepared in several steps from L-tartaric acid. On ozonolysis and subsequent aldol condensation, 5 is transformed into 1, a synthon for the A ring of taxol 2.

  DOI：

  10.1021/jo00125a050

文献信息

• Cyclohexenone Construction by Intramolecular Alkylidene C−H Insertion:  Synthesis of (+)-Cassiol
  作者：Douglass F. Taber、Robert P. Meagley、Douglas J. Doren

  DOI：10.1021/jo960973a

  日期：1996.1.1

  We report new procedures for stereoselective cyclopentene and cyclohexenone construction employing the alkylidene carbene C-H insertion reaction. Described are diastereoselective insertion into methylene and enantiospecific insertion into methine C-H bonds. The latter case leads directly to the enantioselective synthesis of (+)-cassiol (1).
• Intramolecular C-H Insertion by an Alkylidene Carbene: Diastereoselective Synthesis of a Taxol A Ring Synthon
  作者：Douglass F. Taber、Rainer Walter、Robert P. Meagley

  DOI：10.1021/jo00099a035

  日期：1994.10

  The first stage in a proposed total synthesis of the clinically effective anticancer agent taxol 1 is reported. A key step in this synthesis is the development of a new procedure for the generation and cyclization of the alkylidene carbene derived from ketone 9, to give cyclopentene 10 (formation of three new carbon-carbon bonds) in 72% yield. Ozonolysis of 10 followed by aldol condensation furnished the crystalline cyclohexenone 4.